The invention relates to novel monobenzenic couplers comprising at least one cationic group Z, Z being chosen from aliphatic chains comprising at least one quaternized unsaturated ring, to the use thereof for the oxidation dyeing of keratin fibres, to dye compositions containing them, and to oxidation dyeing processes using them.
It is known practice to dye keratin fibres, and in particular human hair, with dye compositions containing oxidation dye precursors, in particular ortho-phenylenediamines or para-phenylenediamines, ortho-aminophenols or para-aminophenols and heterocyclic compounds such as diaminopyrazole derivatives, which are generally referred to as oxidation bases. The oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds which, when combined with oxidizing products, can give rise to coloured compounds and dyes by a process of oxidative condensation.
It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or coloration modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds.
The variety of molecules used as oxidation bases and couplers makes it possible to obtain a wide range of colours.
The so-called xe2x80x9cpermanentxe2x80x9d coloration obtained by means of these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must have no toxicological drawbacks and it must allow shades of the desired strength to be obtained and have good resistance to external agents (light, bad weather, washing, permanent-waving, perspiration and friction).
The dyes must also allow white hairs to be covered, and, lastly, they must be as unselective as possible, i.e. they must allow the smallest possible differences in coloration to be produced over the entire length of the same keratin fibre, which may indeed be differently sensitized (i.e. damaged) between its tip and its root.
It has already been proposed, in particular in patent application FR-A-2 520 358,to use certain cationic derivatives of meta-phenylenediamines, i.e. more specifically, certain meta-phenylenediamines monosubstituted with a quaternized aliphatic chain, for the oxidation dyeing of keratin fibres in intense shades. However, the use of the meta-phenylenediamines described in that prior patent application does not make it possible to obtain a wide variety of colours and, furthermore, the colorations obtained are not always entirely satisfactory as regards their resistance with respect to the various attacking factors to which the hair may be subjected (the action of light, perspiration, shampooing, etc.).
The Applicant has now discovered, entirely surprisingly and unexpectedly, that certain novel monobenzenic compounds of formula (I) defined below comprising at least one cationic group Z, Z being chosen from aliphatic chains comprising at least one quaternized unsaturated ring, are not only suitable for use as couplers for oxidation dyeing, but also make it possible to obtain dye compositions which give intense colorations, in a very wide range of shades, and which have excellent properties of resistance to the various treatments to which the keratin fibres may be subjected. Finally, these compounds are found to be easy to synthesize.
These discoveries form the basis of the present invention.
A first subject of the invention is thus novel compositions of formula (I) below, and the addition salts thereof with an acid: 
in which:
R1, R2 and R3, which may be identical or different, represent a hydrogen atom; a halogen atom; a group Z; a group xe2x80x94COxe2x80x94Z; a group xe2x80x94COxe2x80x94OZ; a (C1-C6)alkylcarbonyl radical; an amino(C1-C6)alkylcarbonyl radical; an Nxe2x80x94Z-amino (C1-C6)alkylcarbonyl radical; an Nxe2x80x94(C1-C6)alkylamino(C1-C6)alkylcarbonyl radical; an N,N-di(C1-C6)alkylamino(C1-C6)alkylcarbonyl radical; an amino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an Nxe2x80x94Z-amino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6) alkylamino (C1-C6) alkylcarbonyl (C1-C6) alkyl radical; an N,N-di(C1-C6)alkylamino(C1-C6)alkyl-carbonyl(C1-C6)alkyl radical; a carboxyl radical; a (C1-C6)alkylcarboxyl radical; a C1-C6 alkylsulphonyl radical; an aminosulphonyl radical; an Nxe2x80x94Z-amino-sulphonyl radical; a C1-C6 N-alkylaminosulphonyl radical; an N,N-di (C1-C6) alkylaminosulphonyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 Nxe2x80x94Z-aminosulphonylalkyl radical; an Nxe2x80x94(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; a carbamyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl radical; an N,N-di(C1-C6)alkylcarbamyl radical; a carbamyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a cyano radical; a group OR6 or SR6; or an amino group protected with a (C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, trifluoro(C1-C6)alkylcarbonyl, amino(C1-C6)alkylcarbonyl, Nxe2x80x94Z-amino(C1-C6)alkylcarbonyl, Nxe2x80x94(C1-C6)alkylamino(C1-C6)alkylcarbonyl, N,N-di(C1-C6)alkylamino(C1-C6)alkylcarbonyl, (C1-C6) alkylcarboxyl, carbamyl, Nxe2x80x94(C1-C6) alkylcarbamyl, N,N-di(C1-C6)alkylcarbamyl, C1-C6 alkylsulphonyl, aminosulphonyl, Nxe2x80x94Z-aminosulphonyl, C1-C6 N-alkylaminosulphonyl, N,N-di(C1-C6)alkylaminosulphonyl, thiocarbamyl or formyl radical, a group xe2x80x94COxe2x80x94Z or a group xe2x80x94COxe2x80x94OZ;
R6 denotes a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a group Z; a (C1-C6)alkoxy(C1-C6)alkyl radical; an aryl radical; a benzyl radical; a carboxy(C1-C6)alkyl radical; a (C1-C6)alkylcarboxy-(C1-C6)alkyl radical; a cyano(C1-C6)alkyl radical; a carbamyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 Nxe2x80x94Z-aminosulphonylalkyl radical; an Nxe2x80x94(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphinyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylcarbonyl(C1-C6)alkyl radical; a C1-C6 aminoalkyl radical; a C1-C6 aminoalkyl radical in which the amine is substituted with one or two identical or different radicals chosen from C1-C6 alkyl, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6)alkylcarbonyl, formyl, trifluoro-(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, carbamyl, Nxe2x80x94(C1-C6)alkylcarbamyl, N,N-di-(C1-C6)alkylcarbamyl, thiocarbamyl and C1-C6 alkylsulphonyl radicals, and from the groups Z, xe2x80x94COxe2x80x94Z and xe2x80x94COxe2x80x94OZ;
A1 represents a group xe2x80x94NR4R5 or a hydroxyl radical;
A2 represents a group xe2x80x94NRxe2x80x24Rxe2x80x25 or a hydroxyl radical;
R4, Rxe2x80x24, R5 and Rxe2x80x25, which may be identical or different, represent a hydrogen atom; a group Z; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C1-C6)alkyl radical; an aryl radical; a benzyl radical; a cyano(C1-C6)alkyl radical; a carbamyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; a thiocarbamyl(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 sulphoalkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyl radical; a (C1-C6)alkylsulphinyl(C1-C6)alkyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 Nxe2x80x94Z-aminosulphonylalkyl radical; an Nxe2x80x94(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylcarbonyl(C1-C6)alkyl radical; a C1-C6 aminoalkyl radical; a C1-C6 aminoalkyl radical in which the amine is substituted with one or two identical or different radicals chosen from C1-C6 alkyl, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6)alkylcarbonyl, carbamyl, Nxe2x80x94(C1-C6)alkylcarbamyl or N,N-di(C1-C6)alkylcarbamyl, C1-C6 alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl and thiocarbamyl radicals, or with a group Z, xe2x80x94COxe2x80x94Z or xe2x80x94COxe2x80x94OZ; one and only one of the radicals R4, Rxe2x80x24, R5 and Rxe2x80x25 can also represent a (C1-C6)alkylcarboxyl radical; a (C1-C6)alkylcarbonyl radical; a formyl radical; a trifluoro(C1-C6)alkylcarbonyl radical; an amino(C1-C6)alkylcarbonyl radical; an Nxe2x80x94Z-amino(C1-C6)alkylcarbonyl radical; an Nxe2x80x94(C1-C6)alkylamino(C1-C6)alkylcarbonyl radical; an N,N-di(C1-C6)alkylamino(C1-C6)alkylcarbonyl radical; a carbamyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl radical; an N,N-di(C1-C6)alkylcarbamyl radical; a thiocarbamyl radical; an aminosulphonyl radical; an Nxe2x80x94Z-aminosulphonyl radical; an Nxe2x80x94(C1-C6)alkylaminosulphonyl radical; an N,N-di(C1-C6)alkylaminosulphonyl radical; a (C1-C6)alkylsulphonyl radical; a group xe2x80x94COxe2x80x94Z or a group xe2x80x94COxe2x80x94OZ;
Z is chosen from the unsaturated cationic groups of formulae (II) and (III) below, and the saturated cationic groups of formula (IV) below: 
xe2x80x83in which:
D is a linker arm which represents a linear or branched alkyl chain preferably containing from 1 to 14 carbon atoms, which may be interrupted by one or more hetero atoms such as oxygen, sulphur or nitrogen atoms, and which may be substituted with one or more hydroxyl or C1-C6 alkoxy radicals;
the ring members E, G, J, L and M, which may be identical or different, represent a carbon, oxygen, sulphur or nitrogen atom;
n is an integer between 0 and 4 inclusive;
m is an integer between 0 and 5 inclusive;
the radicals R, which may be identical or different, represent a group Z, a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a cyano(C1-C6)alkyl radical, a C1-C6 alkoxy radical, a tri(C1-C6)alkylsilane(C1-C6)alkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a (C1-C6)alkylcarbonyl radical, a thio radical, a C1-C6 thioalkyl radical, a C1-C6 alkylthio radical, an amino radical, an amino radical protected with a (C1-C6)alkylcarbonyl, carbamyl or C1-C6 alkylsulphonyl radical; a group NHRxe2x80x3 or NRxe2x80x3Rxe2x80x2xe2x80x3 in which Rxe2x80x3 and Rxe2x80x3xe2x80x2, which may be identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical;
xe2x80x83when n is greater than or equal to 2, two of the adjacent radicals R can also form together an unsaturated 5- or 6-membered carbon-based ring or a ring containing one or more hetero atoms;
R7 represents a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a cyano(C1-C6)alkyl radical, a tri(C1-C6)alkylsilane(C1-C6)alkyl radical, a (C1-C6)alkoxy(C1-C6)alkyl radical, a carbamyl(C1-C6)alkyl radical, a (C1-C6)alkylcarboxy(C1-C6)alkyl radical, a benzyl radical or a group Z of formula (II), (III) or (IV) as defined above;
R8, R9 and R10, which may be identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a (C1-C6)alkoxy(C1-C6)alkyl radical, a cyano(C1-C6)alkyl radical, an aryl radical, a benzyl radical, an amido(C1-C6)alkyl radical, a tri(C1-C6)alkylsilane(C1-C6)alkyl radical or a C1-C6 aminoalkyl radical in which the amine is protected with a (C1-C6)alkylcarbonyl, carbamyl or C1-C6 alkylsulphonyl radical; two of the radicals R7, R8 and R9 can also form, together with the nitrogen atom to which they are attached, a 5- or 6-membered saturated carbon-based ring or a ring containing one or more hetero atoms, such as, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, it being possible for the said ring to be unsubstituted or substituted with a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a cyano(C1-C6)alkyl radical, a C1-C6 alkoxy radical, a tri(C1-C6)alkylsilane(C1-C6)alkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a keto(C1-C6)alkyl radical, a thio radical, a C1-C6 thioalkyl radical, a C1-C6 alkylthio radical, an amino radical or an amino radical protected with a (C1-C6)alkylcarbonyl, carbamyl or C1-C6 alkylsulphonyl radical;
xe2x80x83one of the radicals R8, R9 and R10 can also represent a radical Dxe2x80x2 of a second group Z, Dxe2x80x2 having the same meanings as those indicated above for D;
R11 represents a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a C1-C6 aminoalkyl radical, a C1-C6 aminoalkyl radical in which the amine is protected with a (C1-C6)alkylcarbonyl, carbamyl or C1-C6 alkylsulphonyl radical; a carboxy(C1-C6)alkyl radical; a cyano(C1-C6)alkyl radical; a carbamyl(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a tri(C1-C6)alkylsilane(C1-C6)alkyl radical; a sulphonamido(C1-C6)alkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyl radical; a (C1-C6)alkylsulphinyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylketo(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylsulphonamido(C1-C6)alkyl radical;
x and y are integers equal to 0 or 1; with the following conditions:
xe2x80x83in the unsaturated cationic groups of formula (II):
when x=0, the linker arm D is attached to the nitrogen atom,
when x=1, the linker arm D is attached to one of the ring members E, G, J or L,
y cannot take the value 1 except: 1) when the ring members E, G, J and L simultaneously represent a carbon atom, and when the radical R7 is borne by the nitrogen atom of the unsaturated ring; or alternatively 2) when at least one of the ring members E, G, J and L represents a nitrogen atom to which the radical R7 is attached;
xe2x80x83in the unsaturated cationic groups of formula (III):
when x=0, the linker arm D is attached to the nitrogen atom,
when x=1, the linker arm D is attached to one of the ring members E, G, J, L or M,
y cannot take the value 1 except when at least one of the ring members E, G, J, L and M represents a divalent atom, and when the radical R7 is borne by the nitrogen atom of the unsaturated ring;
xe2x80x83in the cationic groups of formula (IV):
when x=0, then the linker arm is attached to the nitrogen atom bearing the radicals R8 to R10,
when x=1, then two of the radicals R8 to R10 form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring as defined above, and the linker arm B is borne by a carbon atom of the said saturated ring;
Xxe2x88x92 represents a monovalent or divalent anion and is preferably chosen from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogen sulphate and a C1-C6 alkyl sulphate such as, for example, a methyl sulphate or an ethyl sulphate;
it being understood that the number of unsaturated cationic groups Z of formula (II) or (III) is at least equal to 1, and with the exclusion of the compound of the following formula: 
xe2x80x83which is a compound which is known as an intermediate for the manufacture of azo dyes: see in particular patent application DE 1 135 589.
As mentioned above, the colorations obtained with the oxidation dye composition in accordance with the invention are intense and make it possible to obtain a very wide range of colours. Moreover, they have excellent properties of resistance with respect to the action of various external agents (light, bad weather, washing, permanent-waving, perspiration, rubbing). These properties are particularly noteworthy in particular as regards the resistance of the colorations obtained with respect to the action of light.
In formula (I) above, the alkyl and alkoxy radicals may be linear or branched.
Among the rings of the unsaturated groups Z of formula (II) above, mention may be made in particular, by way of example, of pyrrole, imidazole, pyrazole, oxazole, thiazole, triazole, pyrazolopyrimidinium, pyrazolopyridinium, benzoimidazolinium, benzoxazolinium, benzothiazolinium, indolinium, indolidinium, isoindolinium, indazolinium, benzotriazolinium, benzoimidazolidinium and benzopyrimidinium rings.
Among the rings of the unsaturated groups Z of formula (III) above, mention may be made in particular, by way of example, of pyridine, pyrimidine, pyrazine, oxazine, triazine, pyrazolopyrimidinium, pyrazolopyridinium, quinolinium and tetrahydroquinolinium rings. Among the compounds of formula (I) above, mention may be made in particular of:
1-[3-(2,4-diaminophenoxy)propyl]-3-methyl-3H-imidazol-1-ium chloride;
1-[(3-hydroxy-4-methylphenylcarbamoyl)methyl]-3-methyl-3H-imidazol-1-ium chloride;
3-ethyl-1-[(3-hydroxyphenylcarbamoyl)methyl]-3H-imidazol-1-ium chloride;
1-[(3-hydroxy-2,4-dimethylphenylcarbamoyl)methyl]-3-methyl-3H-imidazol-1-ium chloride;
1-[(4-chloro-3-hydroxyphenylcarbamoyl)methyl]-3-methyl-3H-imidazol-1-ium chloride;
1-[(3-hydroxy-4-methoxyphenylcarbamoyl)methyl]-3-methyl-3H-imidazol-1-ium chloride;
1-[(3-hydroxy-4-methylphenylcarbamoyl)methyl]-2-methyl-2H-pyrazol-1-ium chloride;
1-[2-(3-hydroxy-4-methylphenylamino)ethyl]-3-methyl-3H-imidazol-1-ium bromide;
1-[2-(3-hydroxy-4-methylphenylcarbamoyloxy)ethyl]-2,3-dimethyl-3H-imidazol-1-ium chloride;
1-{[3-amino-4-(3-(3-methyl-3H-imidazol-1-ium)propoxy)phenylcarbamoyl]methyl}-3-methyl-3H-imidazol-1-ium dichloride;
3-(3-trimethylammonium-2-hydroxypropyl)-1-[(3-hydroxy-4-methylphenylcarbamoyl)methyl]-3H-imidazol-1-ium dichloride;
1-{[2-(2-(2,4-diaminophenoxy)ethylcarbamoyl]methyl}-3-methyl-3H-imidazol-1-ium chloride;
1-[(2,4-dihydroxyphenylcarbamoyl)methyl]-3-methyl-3H-imidazol-1-ium chloride;
N,N-bis[2-(3-methyl-3H-imidazol-1-ium)ethyl]benzene-1,3-diamine dichloride;
1-{3-[4-amino-2-(2-triethylammoniumacetylamino)phenoxy]propyl}-3-methyl-3H-imidazol-1-ium dichloride;
1-(3-{4-amino-2-[2-(3-methyl-3H-imidazol-1-ium)acetylamino]phenoxy}propyl)-1,4-dimethylpiperazin-1-ium dichloride;
1-[2-(2,4-dihydroxyphenyl)-2-oxoethyl]-3-methyl-3H-imidazol-1-ium chloride;
1-[2-(2,4-diaminophenyl)ethyl]-3-methyl-3H-imidazol-1-ium chloride;
and the addition salts thereof with an acid.
The compounds of formula (I) in accordance with the invention can readily be obtained, according to methods that are well known in the prior art, for example by reducing the corresponding cationic nitro compounds (cationic meta-nitroanilines or cationic meta-nitrophenols).
This reduction step (production of a primary aromatic amine), optionally followed by a salification, is generally, for the sake of convenience, the final step in the synthesis.
This reduction can be carried out earlier in the sequence of reactions leading to the preparation of compounds of formula (I), and according to well-known processes, in which case it is necessary to xe2x80x9cprotectxe2x80x9d the primary amine created (for example by means of an acetylation, benzenesulphonation, etc. step) and then carry out the desired substitution(s) or modification(s) (including quarternization) and end by xe2x80x9cdeprotectingxe2x80x9d (generally in acidic medium) the amine function.
Similarly, the phenolic function can be protected according to well-known processes, by means of a benzyl radical (xe2x80x9cdeprotectionxe2x80x9d by catalytic reduction) or by means of an acetyl or mesyl radical (xe2x80x9cdeprotectionxe2x80x9d in acidic medium).
When the synthesis is complete, the compounds of formula (I) in accordance with the invention can, if necessary, be recovered by methods that are well known in the prior art, such as crystallization or distillation.
Another subject of the invention is the use of the compounds of formula (I) in accordance with the invention as couplers for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
A subject of the invention is also a composition for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, characterized in that it comprises, as coupler, in a medium which is suitable for dyeing, at least one compound of formula (I) in accordance with the invention.
The compound(s) of formula (I) in accordance with the invention and/or the addition salt(s) thereof with an acid preferably represent(s) from 0.0005 to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately relative to this weight.
According to one preferred embodiment of the invention, the dye composition also contains one or more oxidation bases which can be chosen from the oxidation bases conventionally used in oxidation dyeing and among which mention may be made in particular of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the para-phenylenediamines which can be mentioned more particularly, for example, are para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-chloroaniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, Nxe2x80x94(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-Nxe2x80x94(xcex2-hydroxyethyl)-para-phenylenediamine, Nxe2x80x94(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, Nxe2x80x94(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2 -xcex2-hydroxyethyloxy-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine and Nxe2x80x94(xcex2-methoxyethyl)-para-phenylenediamine, and the addition salts thereof with an acid.
Among the para-phenylenediamines mentioned above, the ones most particularly preferred are para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-xcex2-acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid.
Among the bis(phenyl)alkylenediamines which can be mentioned more particularly, for example, are N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis (4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition salts thereof with an acid.
Among the para-aminophenols which can be mentioned more particularly, for example, are para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.
Among the ortho-aminophenols which can be mentioned more particularly, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.
Among the heterocyclic bases which can be mentioned more particularly, for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
When they are used, these oxidation base(s) preferably represent(s) from 0.0005 to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately relative to this weight.
In addition to the compound(s) of formula (I) above, the dye composition in accordance with the invention can also include one or more additional couplers which can be chosen from the couplers used conventionally in oxidation dyeing and among which mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indolene derivatives, pyridine derivatives and pyrazolones, and the addition salts thereof with an acid.
These couplers are chosen more particularly from 2-methyl-5-aminophenol, 5-Nxe2x80x94(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxy-benzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazol-5-one, and the addition salts thereof with an acid.
When they are present, these couplers preferably represent from 0.0001 to 10% by weight approximately relative to the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately relative to this weight.
In general, the addition salts with an acid which can be used in the context of the invention (compounds, of formula (I), additional oxidation bases and couplers) are chosen in particular from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The medium which is suitable for dyeing (or support) generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in water. As organic solvent, mention may be made, for example, of C1-C4 lower alkanols;, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof.
The solvents can be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
The pH of the dye composition in accordance with the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value using acidifying or basifying agents commonly used to dye keratin fibres.
Among the acidifying agents which may be mentioned, for example, are inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.
Among the basifying agents which can be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (V) below: 
in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; R12, R13, R14 and R15, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical.
The oxidation dye compositions in accordance with the invention can also include at least one direct dye, in particular in order to modify the shades or to enrich them with glints.
The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, packaging agents such as, for example, silicones, which may or may not be volatile or modified, film-forming agents, ceramides, preserving agents and opacifiers.
Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the addition(s) envisaged.
The dye composition according to the invention can be in various forms, such as in the form of liquids, creams or gels or in any other form which is suitable for dyeing keratin fibres, and in particular human hair.
The invention also relates to a process for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, using the dye composition as defined above.
According to this process, at least one dye composition as defined above is applied to the fibres, the colour being developed at acidic, neutral or alkaline pH using an oxidizing agent which is added, just at the time of use, to the dye composition, or which is present in an oxidizing composition that is applied simultaneously or sequentially.
According to a preferred embodiment of the dyeing process of the invention, the dye composition described above is preferably mixed, at the time of use, with an oxidizing composition containing, in a medium which is suitable for dyeing, at least one oxidizing agent present in an amount which is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres and is left in place for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which the fibres are rinsed, washed with shampoo, rinsed again and dried.
The oxidizing agent can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibres, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes such as peroxidases and 2-electron oxidoreductases. Hydrogen peroxide is particularly preferred.
The pH of the oxidizing composition containing the oxidizing agent as defined above is such that, after mixing with the dye composition, the pH of the resultant composition applied to the keratin fibres preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It is adjusted to the desired value using acidifying or basifying agents commonly used to dye keratin fibres and as defined above.
The oxidizing composition as defined above can also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
The composition which is finally applied to the keratin fibres can be in various forms, such as in the form of liquids, creams, gels or any other form which is suitable for dyeing keratin fibres, and in particular human hair.
Another subject of the invention is a multi-compartment dyeing device or xe2x80x9ckitxe2x80x9d or any other multi-compartment packaging system, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition as defined above. These devices can be equipped with a means for delivering the desired mixture onto the hair, such as the devices described in patent FR 2 586 913 in the name of the Applicant.